Heterocyclic vat dyestuffs



United States Patent HETEROCYCLIC VAT DYESTUFFS No Drawing. Application December 30, 1955 Serial No. 556,415

12 Claims. (Cl. 260-3461) This invention relates to novel heterocyclic vat dyel5 stuifs having the formula wherein one pair Y-Y' is hydrogen, the other pair Y-Y' is selected from the group consisting of )5 as on on, ofi c-- I at n I fl) N H-R and e r rt A CH 0 g 2,862,931 Patented Dec. 2, 1958 wherein one pair Y-Y' is hydrogen and the other pair Y-Y' is selected from the group consisting of 0 NH: s 2% cfi 011,011 0 l g l I and O NH: o n l cfi o These dyestutt intermediates, and methods for their production are disclosed and claimed in our copending application Serial No. 556,395 filed on even date herewith.

As the vattable polycyclic ketone which may be halogenated, for example chlorinated or brominated, in known manner to provide the above described reactants, there may be mentioned dibenzopyrenequinone, anthanthrone, pyranthrone, dibenzanthrone, isodibenzanthrone, and similar vattable polycyclic ketones well known in the prior art. The nuclearly brominated and chlorinated derivatives of these vattable polycyclic ketones and their methods of production are likewise well known in the prior art.

The reaction is carried out in the presence of an inert organic diluent such as an aromatic hydrocarbon or halogenated aromatic hydrocarbon. As representative of such diluents, there may be mentioned nitrobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, naphthalene, and the like.

The reaction between the halogenated vattable polycyclic ketone and the above described dyestufi intermediate is carried out in the presence of an alkaline acid binding agent, such as sodium carbonate, potassium carbonate, and the like, and a copper catalyst which may be copper in any form, copper oxide, cuprous chloride, cupric acetate, and the like.

The temperature at which the reaction may be carried out will be dependent upon the particular components present in the reaction mixture, and the diluent employed. Generally, elevated temperatures are preferred, which for example may range from about to 250 C. The optimum temperature in any particular instance will be readily ascertainable by the worker skilled in the art. It will be similarly apparent that the molar proportions of the reactants to be employed will depend upon the number of halogen atoms in the vattable polycyclic ketone, and the number of free amino groups in the dyestutf intermediate.

Example 1 A charge of 30 parts by volume nitrobenzene, 1.2 parts by weight dibromdibenzopyrenequinone, 1.6 parts by weight of the compound of the structure prepared as described in Example 1 of said copending application, 0.5 parts by weight soda ash and 0.2 parts by weight copper powder was stirred at 200-205" C. for 20 hours. The reaction product was filtered ofi at room temperature, washed with nitrobenzene, acetone, warm water and dried. It has the formula The product dyes cotton from an alkaline hydrosulfite vat strong black-brown shades of good fastness to washing, chlorine and light.

Example 2 A charge of 30 parts by volume nitrobenzene, 1.2 parts by weight dibromdibenzopyrenequinone, 1.6 parts by weight of the compound of the structure prepared as described in Example 2 of said copending a weight copper powder was reacted and worked up as described in Example 1.

The reaction product has the formula It dyes cotton from an alkaline hydrosulfite vat strong black shades of good fastness to washing, chlorine and light.

Example 3 A charge of 30 parts by volume nitrobenzene, 0.7 parts by weight dibromanthanthrone, 1.0 parts by weight of the compound of the structure 0.3 part by weight soda ash and 0.1 part by weight copper powder was reacted and worked up as described in Example 1.

' The reaction product has the formula:

It dyes cotton from an alkaline hydrosulfite vat tinted gray shades of good fastness to washing. chlorine application, 0.5 part by weight soda ash and (L2 P n y T 15 g t Example4 A charge of 45 parts by volume nitrobenzene, 2.9 parts by weight tetrabrompyranthrone, 5.0 parts by weight of the compound of the structure 1.7 parts by weight soda ash and 0.5 part by weight copper powder was reacted and worked up as described in Example 1.

The reaction product has the formula 0 p II NE NH O NE NH O l I] It dyes cotton from an alkaline hydrosulfite vat neutral gray shades of good fastness to washing, chlorine and light.

Example 5 A charge of parts by volume nitrobenzene, 1.4 parts by weight tribromisoviolanthrone, 2.1 parts by weight of the compound of the structure- 0.6 part by weight soda ash and 0.2 part by weight copper powder was stirred at 200-205 C. for 8 hours and worked up as described in Example 1.

The reaction product has the formula:

It dyes cotton from an alkaline hydrosulfite vat blue shades of good fastness to washing, chlorine and light.

This invention has been disclosed with respect to certain preferred embodiments, and various modifications and variations thereof will become obvious to the person I skilled in the art. It is to be understood that such modifications and variations are to be included Within the spirit and purview of this application and the scope of the appended claims. The dyestufis of the instant invention, produced as above described from vattable ketones containing more than 3 fused rings, have good wash-, lightand chlorine fastness.

We claim:

1. Compounds having the formula V 9,802,981: 7 8 wherein one pair Y-Y is hydrogen, the other pair Y--Y' 3. A compound having the formula is selected from the group consisting of o mr-n 5 CE /C5 O 0? on, (iifi c in g and o NH-R 15 o (L A cn o o and R is a nuclearly bonded residue of a vattabie polycyclic ketonc selected from the group consisting of dibenzopyrcnequinone, anthanthronc, pyranthrone, dibenz- 25 4' Ampound having the formula anthrone and isodibcnzanthrone.

2. A compound having the formula 5. A compound having the formula 6. Acompound having the formula 8. A process comprising reacting dibromdibenzopyrenequinone with a compound having the formula NH 6 NH:

in the presence of soda ash and copper and at an elevated temperature of about 100-250 C.

9. A process comprising reacting dibromdibenzopyrenequinone with a compound having the formula l I 0 NH: d

in the presence of soda ash and copper and at an elevated temperature of about 100-250 C.

10. A process comprising reacting dibromanthanthrone 7. A process comprising reacting a nuclearly halo subwith a compounding having the formula stituted vattable polycyclic ketone selected from the group consisting of dibenzopyrenequinone, anthanthrone, pyranthrone, dibenzanthrone and isodibenzanthrone, with 0 a dyestuff intermediate of the formula I 0 O NH2 0 in the presence of soda ash and copper and at an elevated temperature of about 100-250 C. A 11. A process comprising reacting tetrabrompyranth- NH: X

rone with a compound having the formula wherein one pair YY is hydrogen and the other pair 0 YY' is selected from the group consisting of II o 0 NH: )5 we ofi n on c- NH: H)

OH in the presence of soda ash and copper and at an elevated temperature of about IOU-250 C.

It 12. A process comprising reacting tribromisodibenzanthrone with a compound having the formula and O NH: O o

C I II 05 0\ I NH:

in the presence of soda ash and copper and at an elevated in the presence of an alkaline acid binding agent and a temperature of about -250 C. copper catalyst and at an elevated temperature of about IOU-250 C. No references cited. 

1. COMPOUNDS HAVING THE FORMULA 